Filter Media For Respiratory Protection

ABSTRACT

A filter media composition includes a ferrihydrite material having an average pore size (BJH) in a range from 1 to 3 nm and a surface area (BET) of at least 200 m 2 /g or at least 250 m 2 /g or at least 300 m 2 /g.

BACKGROUND

Sorbents used in respiratory filter cartridges are typically based uponactivated carbon. An attribute of activated carbon is its ability toadsorb organic vapors (OV). Activated carbons, although high in surfacearea, are generally unable to adsorb low boiling point polar compoundssuch as ammonia, thus some type of impregnant is used to react and trapthe contaminant.

In order to filter other contaminant gases (hazardous' gases, e.g.acidic gases, ammonia, cyanides, aldehydes), chemicals are added to theactivated carbon in a process known as impregnation. For example, theLewis acidic transition metal salt ZnCl₂ is added to carbon to produce asorbent for ammonia removal. Impregnation of any support (e.g.,activated carbon) involves a balance of loading a sufficient amount ofthe reactive impregnant without destroying the high surface area of thesupport.

When considering inorganic materials as sorbent components, factors suchas toxicity, stability under relevant conditions, and cost represent keyattributes. Traditional carbon impregnants based upon copper and zincare often oxides in the 2+ oxidation state, formed via thermolysis (atca. 180-200° C.) of activated carbons treated with Cu and/or Zn saltsthat are soluble in aqueous or ammoniacal solutions. These inorganicmaterials alone, however, each commonly suffer from low porosity andsurface area.

There are over a dozen known iron oxides including hydrated andhydroxide-containing materials. Generally, these compounds exist innature and may also be synthesized in a laboratory. Iron oxides withhigh porosity and surface area are usually prepared using non-aqueoussolvents, templating reagents, and high calcination temperatures. Anaturally occurring iron oxide mineral known as ‘two-line’ ferrihydrite(henceforth referred to as ferrihydrite) is composed of nanocrystallineaggregates and is characterized by two poorly defined, broadened maximain x-ray diffraction (XRD) methods.

SUMMARY

The present disclosure relates to filter media for respiratoryprotection. In particular the filter media is an unsupportedferrihydrite material that is capable of removing hazardous gases from arespiratory airstream. The ferrihydrite material can be prepared usinglow temperature, aqueous based processes and can be a doped material.

In one aspect, a composition includes a doped ferrihydrite materialhaving an average pore size (BJH) in a range from 1 to 3 nm and asurface area (BET) of at least 200 m²/g or at least 250 m²/g or at least300 m²/g.

In another aspect, a respiratory protection filter includes a housinghaving an air stream inlet and an air stream outlet and containing anamount of filtration media in fluid connection and between the airstream inlet and the air stream outlet. The filtration media includesfree-standing granular doped ferrihydrite material.

In a further aspect, a method includes combining a hydrated iron (III)salt with a metal dopant salt to form a mixture and blending abicarbonate material with the mixture to form a wet doped ferrihydritematerial and salt co-product. Then the method includes drying the wetdoped ferrihydrite material and salt co-product to a moisture content ofless than 10% by wt or less than 5% by wt to form a dried dopedferrihydrite material and salt co-product. Then, washing away the saltco-product with water to form a wet doped ferrihydrite material anddrying the wet doped ferrihydrite material to a moisture content of lessthan 10% by wt or less than 5% by wt to form a dried doped ferrihydritematerial.

These and various other features and advantages will be apparent from areading of the following detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

The disclosure may be more completely understood in consideration of thefollowing detailed description of various embodiments of the disclosurein connection with the accompanying drawings, in which:

FIG. 1 is a schematic drawing of an illustrative respiratory protectionfilter; and

FIG. 2 is a flow diagram of an illustrative method.

DETAILED DESCRIPTION

In the following detailed description, reference is made to theaccompanying drawings that form a part hereof, and in which are shown byway of illustration several specific embodiments. It is to be understoodthat other embodiments are contemplated and may be made withoutdeparting from the scope or spirit of the present disclosure. Thefollowing detailed description, therefore, is not to be taken in alimiting sense.

All scientific and technical terms used herein have meanings commonlyused in the art unless otherwise specified. The definitions providedherein are to facilitate understanding of certain terms used frequentlyherein and are not meant to limit the scope of the present disclosure.

Unless otherwise indicated, all numbers expressing feature sizes,amounts, and physical properties used in the specification and claimsare to be understood as being modified in all instances by the term“about.” Accordingly, unless indicated to the contrary, the numericalparameters set forth in the foregoing specification and attached claimsare approximations that can vary depending upon the properties desiredby those skilled in the art utilizing the teachings disclosed herein.

The recitation of numerical ranges by endpoints includes all numberssubsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3,3.80, 4, and 5) and any range within that range.

As used in this specification and the appended claims, the singularforms “a”, “an”, and “the” encompass embodiments having pluralreferents, unless the content clearly dictates otherwise.

As used in this specification and the appended claims, the term “or” isgenerally employed in its sense including “and/or” unless the contentclearly dictates otherwise.

As used herein, “have”, “having”, “include”, “including”, “comprise”,“comprising” or the like are used in their open ended sense, andgenerally mean “including, but not limited to”. It will be understoodthat “consisting essentially of”, “consisting of”, and the like aresubsumed in “comprising,” and the like.

The term “free-standing” material refers to an unsupported material or amaterial that is not impregnated onto a support material.

The present disclosure relates to filter media for respiratoryprotection. In particular the filter media is an unsupportedferrihydrite material that is capable of removing reactive gases from arespiratory airstream. The ferrihydrite material can be formed using lowtemperature, aqueous based processes and can be a doped material. Theferrihydrite material has an average pore size in a range from 1 to 3 nm(BJH method) and a surface area of at least 200 m²/g or at least 250m²/g or at least 300 m²/g (BET method). Filtration media within arespiratory protection filter has at least 20% by wt, or at least 30% bywt, or at least 50% by wt ferrihydrite material. The ferrihydritematerial can be formed at temperatures below 115 degrees centigrade orbelow 110 degrees centigrade. Forming the ferrihydrite material includesat least one drying step that removes only water or moisture. Theferrihydrite material is granulated to a mesh size in a range from 12 to50 U.S. standard sieve series. While the present disclosure is not solimited, an appreciation of various aspects of the disclosure will begained through a discussion of the examples provided below.

FIG. 1 is a schematic drawing of an illustrative respiratory protectionfilter 10. The respiratory protection filter 10 includes a housing 20having an air stream inlet 22 and an air stream outlet 24 and containingan amount of filtration media 30 in fluid connection and between the airstream inlet 22 and the air stream outlet 24. The filtration media 30includes free-standing granular doped ferrihydrite material. In manyembodiments, the filtration media 30 includes at least 20% wt or atleast 30% wt or at least 50% wt ferrihydrite material or dopedferrihydrite material.

The filtration media 30 can include one or more additional types offiltration material, such as, activated carbon, for example. Theferrihydrite material is not impregnated onto a support material, suchas activated carbon, for example.

The ferrihydrite material is capable of removing hazardous gas from anair stream passing through the filtration media 30 at ambient conditionsor atmospheric pressure and −20 to 40 degrees centigrade and 5% to 95%relative humidity. These hazardous gases include both acidic and basicgases.

The ferrihydrite material described herein has an average pore size (BJHmethod) in a range from 1 to 3 nm and a surface area (BET) of at least200 m²/g or at least 250 m²/g or at least 300 m²/g. The dopedferrihydrite material has a molar ratio of iron:dopant in a range from95:5 to 75:25 or from 90:10 to 80:20.

The ferrihydrite material can be doped with a dopant material comprisinga metal such as Cu, Zn, Ca, Ti, Mg, Zr, Mn, Al, Si, Mo, Ag or mixturesthereof forming a doped ferrihydrite material. Dopants may be secondarymetal oxides that are incorporated into the iron oxide for beneficialeffect. In many embodiments, the doped ferrihydrite material includesCu, Zn and/or Mn as dopant materials. The doped ferrihydrite materialhas a moisture content of less than 10% by wt or less than 5% by wt.

The ferrihydrite material forms a powder material that defines aggregateparticles having a median largest lateral dimension in a range from 1 to100 micrometers or from 15 to 45 micrometers or from 20 to 40micrometers or about 30 micrometers. These particles are granulated todefine granules having a mesh size in a range from 12 to 50 or from 20to 40. Any useful granulation process can be utilized. In manyembodiments, the granules are formed with compression and without theuse of a binder. The ferrihydrite granules have a moisture content ofless than 10% wt or less than 5% wt.

FIG. 2 is a flow diagram of an illustrative method 100. The methodincludes combining a hydrated iron (III) salt with a metal dopant saltto form a mixture (powder mixture) at block 110 and blending abicarbonate material (preferably a powder sodium bicarbonate) with themixture to form a wet doped ferrihydrite material and salt co-product atblock 120. Then drying the wet doped ferrihydrite material and saltco-product to a moisture content of less than 10% by wt or less than 5%by wt to form a dried doped ferrihydrite material and salt co-product atblock 130. The salt co-product is washed away to form a wet dopedferrihydrite material at block 140. The wet doped ferrihydrite materialis dried to a moisture content of less than 10% by wt or less than 5% bywt to form a dried doped ferrihydrite material at block 150. The dopedferrihydrite material at block 160 is then granulated to form agranulated filtration media product at block 170.

The method 100 occurs at relatively low temperatures. In manyembodiments the method 100 has a processing temperature for all thesteps that is no greater than 115 degrees centigrade or no greater than110 degrees centigrade. In many embodiments, the drying steps 130, 150removes only water or moisture from the wet doped ferrihydrite materialand salt co-product or the wet doped ferrihydrite material.

A general illustrative procedure for the preparation of the dopedferrihydrite material described herein involves:

(i) The combination and mixing of solid Fe(NO₃)₃.9H₂O and another metalsalt (e.g. Cu, Zn, Mn, Al) in an appropriate stoichiometric ratio, in amixing vessel. The powders are mixed so that they appear to be afree-flowing (e.g., no obvious lumps) powder and relatively homogeneous.

(ii) The addition of free-flowing bicarbonate powder in an appropriateratio.

(iii) The resulting powder mixture is then ground together eithermanually or with mechanical stirring to mix the reagents. This mixturebecomes frothy (CO₂ evolution and water release) over the course of thereaction and gradually darkens to a red-orange slurry. Mixing continuesuntil gas evolution ceases. After this time period the stirred mixturethickens to a solid brownish solid.

(iv) The resulting brown material is placed in an oven at 100-105° C.for a period of time to dry to less than 10% by wt water. After thistime period, nitrate salts and possible other co-products are observedin the dried material.

(v) The solid is then transferred to a filtration apparatus and washedwith an appropriate amount of water to rid the solid of water-solublesalt co-products.

(vi) The washed material is placed in an oven at 100-105° C. for aperiod of time to dry to less than 10% by wt or less than 5% by wtwater. This product has a brownish color.

An additional procedure for the preparation of doped ferrihydritematerial involves the precipitation of iron and secondary metal saltsdissolved together in an aqueous solution. This is accomplished byraising the pH of the acidic metal salt solution to pH 7-8 by theaddition of a base, as described in Example 6 below. This method mayform more heavily aggregated materials than Examples 1-5, resulting inlarger particle sizes as reported in Table 2.

Objects and advantages of this disclosure are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this disclosure.

EXAMPLES

All parts, percentages, ratios, etc. in the examples are by weight,unless noted otherwise. Solvents and other reagents used are obtainedfrom Sigma-Aldrich Corp., St. Louis, Mo. unless specified differently.

Material Listing

Unless otherwise indicated, Fe(NO₃)₃.9H₂O, Cu(NO₃)₂.2.5H₂O,Zn(NO₃)₂.6H₂O, Fe₂(SO₄)₃.2.5H₂O, CuSO₄.5H₂O, NaOH, NH₄HCO₃, and NaHCO₃were obtained in reagent grade from Sigma-Aldrich Co. (St. Louis, Mo.,USA).

Example 1

Un-doped ferrihydrite was prepared according to the procedure given inInorg. Chem. 51 (2012) 6421. In summary, 0.05 mol Fe(NO₃)₃.9H₂O wascombined with 0.15 mol of NH₄HCO₃ for 30 minutes in a mortar and pestle.After drying the resulting product for 14 hours at 100° C. in a mufflefurnace under static air, the material was washed with three 50 mLportions of deionized water using a 5 cm diameter Buchner funnel andvacuum filter apparatus equipped with Fisherbrand filter paper (mediumporosity, Grade P5). The filtered solid was then dried at 100° C. for 14hours to a moisture content of less than 5 wt. %. The resulting materialwas then formed into pellets using a 13 mm die and Carver press using apressure of 70000 PSI. The pellets were then crushed and sized to 20×40mesh granules.

Example 2

Un-doped ferrihydrite was prepared using a similar procedure to Example1, with the exception that NaHCO₃ was used instead of NH₄HCO₃. NaHCO₃was added to pre-ground Fe(NO₃)₃.9H₂O with stirring over the course ofapproximately 30 seconds. The powder mixture became reddish orange andcarbon dioxide gas evolution was noticed during stirring over the courseof the first few minutes. Manual stirring with the pestle was continuedfor approximately 25 minutes until the dark brown slurry hardened andgas evolution was no longer noticeable. The solid mixture was then driedand placed in an oven set at 100° C. After 14 hours, the dried solidappeared to have a white powder coating on top of the clumped material.The solid was filtered, washed and dried and formed into granules in ananalogous fashion to Example 1.

Example 3

Copper-doped ferrihydrite was prepared with an initial Cu:Fe molar ratioof 1:9. The pre-ground powders Fe(NO₃)₃.9H₂O (909 g, 2.25 mol),Cu(NO₃)₂.2.5H₂O (59.7 g, 0.25 mol) and NaHCO₃ (609 g, 7.25 mol) wereweighed into separate containers. The copper(II) nitrate was thencombined with the iron(III) nitrate in a 4L stainless steel bowl and thepowders were mixed intimately for several minutes with a pestle. Afteraddition of the sodium bicarbonate, the powder mixture became reddishorange and carbon dioxide gas evolution was noticed during stirring overthe course of the first few minutes. Manual stirring with the pestle wascontinued for approximately 45 minutes until the dark brown slurryhardened and gas evolution was no longer noticeable. The solid mixturewas then dried and placed in a forced air oven set at 100° C. for 14hours, after which time the dried solid appeared to have a white powdercoating on top of the clumped material. The solid was then transferredto an 11 cm diameter Buchner funnel fitted with Fisherbrand filter paper(coarse porosity, Grade P8). After attachment of the funnel to a vacuumfiltration flask, the solid was washed with deionized water (3.5 L in500 mL portions). The solid was filtered and dried to a moisture contentof less than 5 wt. % and formed into granules in an analogous fashion toExample 1.

Example 4

Copper-doped ferrihydrite was prepared with an initial Cu:Fe molar ratioof 1:4 in an analogous procedure to Example 3, with the exception thatNH₄HCO₃ was used in place of NaHCO₃. After the first drying step, thedried solid appeared to have some bluish-white crystals deposited on thetop surface. Instead of a colorless wash as observed in Example 3, abluish colored filtrate was observed for the first 2 L of wash waterused. The filtered solid was dried to a moisture content of less than 5wt. % and formed into granules in an analogous fashion to Example 1.

Example 5

Zinc-doped ferrihydrite was prepared with an initial Zn:Fe molar ratioof 1:4 in an analogous procedure that led to Example 4, with theexception that Zn(NO₃)₂.6H₂O was used in place of Cu(NO₃)₂.2.5H₂O, and6.75 mol of NH₄HCO₃ was used instead of 7.25 mol. Instead of a blue washas observed in Example 4, an orange colored wash was observed. Thefiltered solid was dried to a moisture content of less than 5 wt. % andformed into granules in an analogous fashion to Example 1.

Example 6

Copper-doped ferrihydrite was prepared with an initial Cu:Fe ratio of1:9. A solution of Fe₂(SO₄)₃.2.5H₂O (50.6 g, 0.10 mol) was prepared in500 mL deionized water. A separate solution of CuSO₄.5H₂O (5.74 g, 0.023mol) was prepared in 500 mL deionized water. These solutions were thenadded to a 2000 mL beaker and stirred magnetically. After 5-10 minutesof mixing, 3.0 mol/L NaOH solution was added dropwise using aMasterFlex© peristaltic pump at a flow rate of approximately 3.4 mL/min.The flow of NaOH was terminated after 227 mL was added and the pH of thereaction mixture was approximately 7. The mixture was left to stir for1.5 hours after the base addition was complete. Stirring was thenstopped and the mixture was left to settle overnight for 16 hours. Amajor portion (approximately 70% by reaction mixture volume) of theresulting supernatant was decanted from the beaker, and the remainingcontents were then transferred to an 11 cm diameter Buchner funnelfitted with Fisherbrand filter paper (coarse porosity, Grade P8). Afterattachment of the funnel to a vacuum filtration flask, the solid waswashed with deionized water (750 mL in 250 mL portions). The solid wasfiltered and dried to a moisture content of less than 10 wt. %. Thedried material was crushed and sized to 20×40 mesh granules.

Testing Methods Tube Testing

A tube testing apparatus was used for breakthrough testing. The sampletubes employed are composed of polyvinylchloride (PVC) (innerdiameter=6.5 mm) with a fine stainless steel mesh near the base. Thesetubes are loaded with a specified volume of filter media granules fortesting and are packed to a constant volume by repeatedly tapping thelower end against a hard surface. The sample tube is connected toflexible Teflon tubing using ultra-torr (Swagelok) fittings. Challengegases of desired concentrations are then delivered through the verticaltube through the top (inlet) portion of the tube at a specified flowrate and the effluent gas that exits the sorbent bed through the lowerend of the tube (outlet) is then transported to a detector for analysis.

SO₂ Breakthrough Testing:

A sample of filter media granules, either obtained from a commercialvendor or prepared according to a given example, equating to a volume ofeither 1 or 1.7 cc was transferred to the tube testing apparatusoutlined above and weighed. In this case the outlet gas stream wasanalyzed by a MIRAN SapphIRe IR portable air analyzer. The filter mediagranules were “tapped” until no significant reduction in volume wasobserved by the human eye. The sample in the tube was then exposed to atest stream of approximately 200 mL/minute of conditioned air (<15% RH)that contained about 1000 ppm of sulfur dioxide (SO₂) in air from acertified gas mixture from Linde (Whitby, ON, Canada). The airdownstream from the filter media granules was monitored for breakthroughusing a MIRAN SapphIRe IR portable air analyzer. The breakthrough timewas defined as the time at which a concentration of 20 ppm was observeddownstream from the sample.

NH₃ Breakthrough Testing:

A sample of filter media granules, either obtained from a commercialvendor or prepared according to a given example, equating to a volume ofeither 1 or 1.7 cc was transferred to the tube testing apparatusoutlined above and weighed. In this case the outlet gas stream wasanalyzed by a MIRAN SapphIRe IR portable air analyzer. The filter mediagranules were “tapped” until no significant reduction in volume wasobserved by the human eye. The sample in the tube was then exposed to atest stream of approximately 200 mL/minute of conditioned air (<15% RH)that contained about 1000 ppm of ammonia (NH₃) in air from a certifiedgas mixture from Linde (Whitby, ON, Canada). The air downstream from thefilter media granules was monitored for breakthrough using a MIRANSapphIRe IR portable air analyzer. The breakthrough time was defined asthe time at which a concentration of 20 ppm was observed downstream fromthe sample.

HCN Breakthrough Testing:

A sample of filter media granules, either obtained from a commercialvendor or prepared according to a given example, equating to a volume of1.7 cc was transferred to the tube testing apparatus outlined above andweighed. In this case the outlet gas stream was analyzed by a gaschromatograph with a flame ionization detector (GC-FID). The filtermedia granules were “tapped” until no significant reduction in volumewas observed by the human eye. The sample in the tube was then exposedto a test stream of approximately 260 mL/minute of conditioned air (<15%RH) that contained about 2000 ppm of hydrogen cyanide (HCN). The airdownstream from the filter media granules was monitored for breakthroughusing a GC-FID system for both HCN, the challenge gas, and cyanogen(NCCN), a common reaction product of HCN. The breakthrough time wasdefined as the time at which a concentration of 5 ppm HCN or NCCN wasobserved downstream from the sample.

Powder X-Ray Diffraction:

Powder X-ray diffraction patterns were collected using a Phillips PW1720 X-ray generator operated at a voltage of 40 kV and a current of 30mA. The system is equipped with a Cu Kα radiation source(wavelength=1.54178 Å) and a diffracted beam monochromator. Typicalconditions were a scan rate of 0.05°/step and a dwell time of 40 s/step.The samples were ground into fine powder and mounted on an aluminumsample holder.

Surface Area and Pore Size Measurements:

N₂ adsorption isotherm and the pore size distribution were determinedusing a Micromeritics ASAP2010 at 77K. Samples were degassed at 100° C.for 2-3 days before the measurement to remove residual moisture. Poresize distributions were determined using the BJH method (1-300 nm) usingsoftware supplied by Micromeritics (ASAP 2010 V5.03 C). The BJH methodis a known method and is described at E. P. Barrett, L. G. Joyner, P. H.Halenda, J. Am. Chem. Soc. 73 (1951) 373.

Particle Size Measurements:

Particle size measurements (d(0.1), d(0.5) and d(0.9)) were made on aMastersizer 2000 (Ver. 5.60) equipped with a Hydro2000S accessory fromMalvern Instruments following 2 minutes of sonication using deionizedwater as a dispersant.

TABLE 1 Selected Characterization Data for Examples 1-5. BJH BJH BETAverage Average Particle Size Surface Pore Pore d(0.1, 0.5, 0.9) Phaseby Area Volume Size Example (μm) XRD (m²/g) (cm³/g) (nm) 1  7.4, 27.0,58.1 2-line 302.5 0.13 2.1 ferrihydrite 2 12.0, 29.2, 56.3 2-line 289.00.17 2.2 ferrihydrite 3 11.8, 28.4, 53.5 2-line 305.2 0.14 2.1ferrihydrite 4 10.9, 31.2, 64.0 2-line 329.9 0.14 1.9 ferrihydrite 511.0, 34.2, 75.5 2-line 276.8 0.085 1.7 ferrihydrite

TABLE 2 Selected Characterization Data for Examples 6. BJH BJH BETAverage Average Particle Size Phase Surface Pore Pore d(0.1, 0.5, 0.9)by Area Volume Size Example (μm) XRD (m²/g) (cm³/g) (nm) 6 8.7, 127.7,2-line 366.7 0.25 2.7 615.9 ferrihydrite

The samples of Examples 1-5 were challenged with vapors or gases usingthe test methods described above. The test results are shown below inTable 3 along with the test results from commercially available CalgonURC, a whetlerite multigas adsorbant prepared by impregnation ofactivated carbon with copper compounds, molybdenum compounds and saltsof sulfuric acid.

TABLE 3 Breakthrough Test Results Breakthrough Time (minutes)⁵ SO₂ NH₃HCN NCCN Example^(1,2,3) (±10%) (±10%) (±6%) (±6%) Calgon URC⁴ 44 52 111105 1 97 110 6 21 (0.6 ppm) 2 156 69 35 53 (0.4 ppm) 3 165 113 106 100 4165 173 165 153 5 67 275 15 12 ¹All filter media granules tested at 20 ×40 mesh size. ²Sample volume: 1 cc (SO₂, NH₃); 1.7 cc (HCN/NCCN)³Average of 3 tests for breakthrough times ⁴Calgon URC (as received),commercially available from Calgon Carbon Company, Pittsburgh, PA, USA.⁵For samples where NCCN was not observed to reach breakthroughconcentration during HCN testing, NCCN breakthrough time is listed withthe detected concentration of NCCN at the end of the test inparenthesis.

TABLE 4 Breakthrough Test Results Breakthrough Time (minutes)⁵ SO₂ NH₃HCN NCCN Example^(1,2,3) (±10%) (±10%) (±6%) (±6%) Calgon URC⁴ 44 52 111105 6 220 80 123 133 ¹All filter media granules tested at 20 × 40 meshsize. ²Sample volume: 1 cc (SO₂, NH₃); 1.7 cc (HCN/NCCN) ³Average of 3tests for breakthrough times ⁴Calgon URC (as received), commerciallyavailable from Calgon Carbon Company, Pittsburgh, PA, USA. ⁵For sampleswhere NCCN was not observed to reach breakthrough concentration duringHCN testing, NCCN breakthrough time is listed with the detectedconcentration of NCCN at the end of the test in parenthesis.

Thus, embodiments of FILTER MEDIA FOR RESPIRATORY PROTECTION aredisclosed.

All references and publications cited herein are expressly incorporatedherein by reference in their entirety into this disclosure, except tothe extent they may directly contradict this disclosure. Althoughspecific embodiments have been illustrated and described herein, it willbe appreciated by those of ordinary skill in the art that a variety ofalternate and/or equivalent implementations can be substituted for thespecific embodiments shown and described without departing from thescope of the present disclosure. This application is intended to coverany adaptations or variations of the specific embodiments discussedherein. Therefore, it is intended that this disclosure be limited onlyby the claims and the equivalents thereof. The disclosed embodiments arepresented for purposes of illustration and not limitation.

1. A composition comprising: a doped ferrihydrite material having anaverage pore size (BJH method) in a range from 1 to 3 nm and a surfacearea (BET) of at least 200 m²/g or at least 250 m²/g or at least 300m²/g.
 2. The composition according to claim 1, wherein the dopedferrihydrite material has a molar ratio of iron:dopant in a range from95:5 to 75:25 or from 90:10 to 80:20.
 3. The composition according toclaim 1, wherein the doped ferrihydrite material includes dopantmaterial comprising a metal such as Cu, Zn, Ca, Ti, Mg, Zr, Mn, Al, Si,Mo, Ag or mixtures thereof.
 4. The composition according to claim 1,wherein the doped ferrihydrite material includes dopant material beingCu or Zn.
 5. The composition according to claim 1, wherein the dopedferrihydrite material are granules having a mesh size in a range from 12to 50 or from 20 to 40 U.S. standard sieve series.
 6. The compositionaccording to claim 1, wherein the doped ferrihydrite material are in aform of compression derived granules.
 7. The composition according toclaim 1, wherein the doped ferrihydrite material defines aggregateparticles having a median largest lateral dimension in a range from 1 to100 micrometers or from 15 to 45 micrometers or from 20 to 40micrometers or about 30 micrometers.
 8. The composition according toclaim 1, wherein the doped ferrihydrite material has a moisture contentof less than 10% by wt or less than 5% by wt.
 9. A respiratoryprotection filter comprising: a housing having an air stream inlet andan air stream outlet and containing an amount of filtration media influid connection and between the air stream inlet and the air streamoutlet, the filtration media comprising: free-standing granular dopedferrihydrite material.
 10. The respiratory protection filter accordingto claim 9, wherein the doped ferrihydrite material is capable ofremoving a hazardous gas from an air stream passing through thefiltration media at ambient conditions or atmospheric pressure and −20to 40 degrees centigrade and 5% to 95% relative humidity.
 11. Therespiratory protection filter according to claim 9, wherein thefiltration media comprises at least 20% by wt or at least 30% by wt orat least 50% by wt doped ferrihydrite material.
 12. The respiratoryprotection filter according to claim 9, wherein the doped ferrihydritematerial has a molar ratio of iron:dopant in a range from 95:5 to 75:25or from 90:10 to 80:20
 13. The respiratory protection filter accordingto claim 9, wherein the doped ferrihydrite material includes dopantmaterial comprising a metal such as Cu, Zn, Ca, Ti, Zr, Mg, Mn, Al, Si,Mo, Ag or mixtures thereof.
 14. The respiratory protection filteraccording to claim 9, wherein the doped ferrihydrite material includesdopant material being Cu or Zn.
 15. The respiratory protection filteraccording to claim 9, wherein the doped ferrihydrite material definesgranules having a mesh size in a range from 12 to 50 or from 20 to 40U.S. standard sieve series.
 16. A method, comprising: combining ahydrated iron (III) salt with a metal dopant salt to form a mixture;blending a bicarbonate material with the mixture to form a wet dopedferrihydrite material and salt co-product; drying the wet dopedferrihydrite material and salt co-product to a moisture content of lessthan 10% by wt or less than 5% by wt to form a dried doped ferrihydritematerial and salt co-product; washing away the salt co-product withwater to form a wet doped ferrihydrite material; and drying the wetdoped ferrihydrite material to a moisture content of less than 10% by wtor less than 5% by wt to form a dried doped ferrihydrite material. 17.The method according to claim 16, wherein the bicarbonate material issodium bicarbonate.
 18. The method according to claim 16, wherein themethod has a processing temperature for all method steps that is nogreater than 115 degrees centigrade.
 19. The method according to claim16, wherein the drying steps removes only water or moisture from the wetdoped ferrihydrite material and salt co-product or the wet dopedferrihydrite material.
 20. The method according to claim 16, wherein themetal dopant salt comprises Cu or Zn. 21-24. (canceled)